WO2012020068A2 - Self-structuring surfaces through pdms phase separations in hard polymer coatings - Google Patents

Abstract

The present invention relates to enamels for coating of surfaces containing a polymer, comprising a base polymer and modifying units which are incompatible with the base polymer after the polymer has cured and lead to the formation of separate phases at the surface, and to processes for production thereof. The enamels have a low coefficient of friction and frictional resistance.

Description

 Self-structuring surfaces through PDMS phase separations in hard polymer coatings

 description

The present invention relates to lacquers for coating surfaces containing a polymer comprising a base polymer and modifying units which, after curing of the polymer, are incompatible with the base polymer and lead to the formation of separate phases on the surface, and methods for their preparation. The paints have a low coefficient of friction and frictional resistance.

Paints are used in various industrial sectors to protect surfaces against external influences such as Moisture, physical stress and weather conditions used. Furthermore, paints are used to increase the lubricity of surfaces. Good lubricity of an article can greatly simplify handling thereof. This is important, for example, in the coating of wires, in particular in their use in electrical components, such as coils. In order to achieve high packing densities of the wires in the coils, the electrical conductors are wound up with automated winding machines. If the electrical conductors have a good slidability, fewer misplacements occur in the coil and thus more efficient coils.

Good lubricity of paints is also important in the coatings of vehicles, eg watercraft, especially ships. Good lubricity in water leads to lower fuel consumption. However, such coatings must also have good anti-fouling and anti-adhesion properties, so that no marine organisms can attach to the hull, which in turn to a reduced lubricity can lead. In addition, a paint for the coating of hulls must be environmentally friendly.

In order to achieve a good lubricity of paints, a coating based on self-crosslinking polyesters and polyesterimides, polyimides and polyamideimides and polyamides and polyesters which are crosslinked with blocked polyisocyanate adducts is conventionally applied first. After applying the actual lacquer layer, a lubricant is applied as outer layer. As lubricants natural waxes, montan waxes, polyethylene waxes and copolymers with propylene polymers of higher α-olefins, polypropylene oxides, esters of higher functional polyols and longer chain fatty acids are used. The use of such lubricants, however, can be problematic for various applications, especially as lubricants based on hydrocarbons, fatty acid esters and polypropylene oxides are not stable at high application temperatures of more than 450 ° C and on the other environmental concerns are questionable. Lubricants based on paraffin wax are usually present as a solution in white spirit. However, such lubricants are problematic due to the vaporizing white spirit for environmental reasons and health reasons.

In WO 2007/045575 a lubricant for enameled wires based on a polytetrafluoroethylene dispersion is described, which should have improved coefficients of friction and is environmentally friendly. However, the lubricant must be applied in a separate process step on the already painted wire.

Another approach to provide coatings with good lubricity, is to mix the paint with a lubricant. Such a lacquer is described, for example, in EP 0 823 120, in which the lacquer contains polyethylene wax as internal lubricant. In another approach to improving the lubricity of paints, the polymers contained in the paint are functionalized with components. EP 0 033 224 and EP 0 072 178 describe electrical insulating coatings based on polymers, for example polyamideimides, which are modified with terminal long-chain alkyl groups.

Furthermore, paints are known in which polysiloxanes are physically mixed into the paint or wherein the polymers contained in the paint are functionalized with polysiloxanes. For example, EP 1 176 611 describes insulated wires comprising a polyamideimide resin terminally modified with alkoxy or aryloxy siloxanes containing a glycidyl ether group. EP 0 447 789 describes insulating lacquers containing a copolymer functionalized with polysiloxanes. There is no further description of the polysiloxane used. DE 20 00 638 (US Pat. No. 3,632,440) likewise describes an insulating material in which polysiloxanes are admixed with a polymer resin or the polymer resin is functionalized by polysiloxanes. A functionalization of the polymer resin with lankettigen polysiloxanes is not shown. US 2003/0215650 describes the modification of polymer compounds with short-chain polysiloxanes. In the case of the above-mentioned paints, however, the components do not produce self-structuring surfaces or cause a phase separation of the paint components.

An object of the invention is to provide a lacquer which has very good surface lubricity combined with high chemical and physical resistance, in particular temperature resistance and flexibility.

This object is achieved in accordance with the invention by providing a surface coating varnish containing a functionalized polymer comprising a base polymer and modifying units that are incompatible with the base polymer after curing, in particular thermal curing, of the polymer. The modifying units are after one Curing or film formation with the base polymer incompatible, so that a self-structuring of the surface takes place. In this case, a phase separate from the base polymer is formed, which is present in particular on the outer surface of the cured paint film and improves the lubricity properties of the paint film. The surface resulting from the self-structuring or phase separation may, among other things, also lead to the generation of microturbulences which, according to the current state of knowledge, may reduce flow resistance in liquid media, eg hulls.

The invention combines the advantageous properties of a base polymer, e.g. chemical stability and / or hardness, with the advantageous properties of the modifying units, e.g. Reduction of adhesion or / and friction reduction. Since the modifying moieties are chemically fixed and, in particular, covalently bonded to the base polymer, the release of the modifying moieties to the environment, and in particular bleeding, is prevented.

The lacquer according to the invention thus has, in particular, a phase separation on the surface, ie separate regions on the surface formed from base polymer, and other separate regions formed from modifying units. It has been found that the cured lacquer according to the invention has a structured anisotropic surface consisting of polar matrix and non-polar separate regions. Differences in mechanical properties have also been noted, namely in particular a rigid polar matrix, in particular a rigid polar base polymer matrix and more preferably a rigid polar polyamideimide matrix and soft, "liquid like" separate regions formed from modifying moieties, especially polysiloxanes, and more preferably PDMS phase separations. Paints are usually present as a dispersion or colloidal solution of polymer particles in a solvent. The polymer particles can be present, for example, in the form of colloidal particles or in the form of gel particles. Gel particles may have modification units on the outside, for example in a brush-like structure. Optionally, other components such as additives are present.

The polymers contained in the paint according to the invention comprise a base polymer which is functionalized or modified with modifying units. The base polymers may e.g. from the group consisting of polyamide-imides, polyester-imides, polyurethanes, polyesters, polyamides, polyimides, polyester-amide-imides, polyepoxides, mixtures or combinations thereof. In a preferred embodiment, the base polymer is a polyamideimide, a polyesterimide or / and a polyurethane, most preferably a polyamideimide. The preparation of such polymers is known.

The base polymer may be selected depending on the desired use. Thus, for example, polyurethanes are used as base polymers for use in anti-fouling or fouling-release applications, in particular for the coating of ship hulls. When used in Elektroisolierlacken preferably find polyamide or or / and polyester imides application.

The polymers according to the present invention contain a base polymer having at least one modifying unit. In particular, the modifying moiety is a polysiloxane, preferably a polydialkylsiloxane, and more preferably a polydimethylsiloxane. The modifying moieties are particularly covalently coupled to the base polymer.

The lacquers contain not only the polymer but also solvents, which are described below. The solids content of the polymer in Electrical insulating lacquer is usually at least 10%, at least 20%, at least 25%, at least 30%, at least 35% and up to 45%, 50%, 60% or 70% (mass / mass). As further constituents, the electrical insulating lacquer may contain additives which are described below.

Surprisingly, it has been found that in the cured lacquer, which is available by curing, in particular thermal curing, separate areas arise on the surface of the cured lacquer. This improves the friction coefficient and the frictional resistance of the cured paints. At the same time, good temperature resistance and flexibility are retained.

Modification units according to the present invention are characterized in that when a lacquer containing a polymer containing such units is applied to a metal plate, e.g. an aluminum plate, or on a glass plate in a thickness of 5 pm to 20 pm and after thermal curing, at a baking temperature of greater than 100 ° C, e.g. 150 ° C, 200 ° C, 220 ° C, 250 ° C or 300 ° C, in particular from 250 ° C and a baking time of 2 to 15 minutes, preferably 10 minutes, separate areas on the surface are present, one of the remaining Surface of the paint film have different topology / structuring. The proportion of these areas with respect to the total surface area can be e.g. determined by atomic force microscopy.

Preferably, the proportion of separate areas on the surface in which there are modifying units, in particular at a proportion of blocks with modifying units of 20 mass% based on the total polymer at least 5 area%, at least 15 area%, at least 20 area%, at least 30 area%, at least 40 area%, at least 50 area% and up to 60 area%, up to 70 area%, up to 80 area%, up to 90 area% or up to 95 area%, with respect to the entire surface. Accordingly, the proportion of areas on the surface in which the base polymer is present is at least 5 area%, at least 15 area%, at least 20 area%, at least 30 area%, at least 40 area%, at least 50 area%. % and up to 60 area%, up to 70 area%, up to 80 area%, up to 90 area% or up to 95 area%, on the whole surface.

The individual separate areas preferably have a characteristic size of at least 0.1 μιτι and preferably of at least 0.2 μιτι on. The size of the separate areas can vary greatly and also in the range of up to several μητι, in particular up to 10 μιη, preferably up to 5 μιη lie.

In one embodiment, the modifying moieties incompatible with the base polymer upon curing or filming are long chain polysiloxanes. Polysiloxanes are chains of silicon atoms linked to oxygen atoms. The free valences of the silicon can be occupied by side chains. In a preferred embodiment, the side chains are independently alkyl, alkoxy, alkenyl, alkynyl, which are optionally substituted by halogen, OH, COOH and / or amino. Preferred side chains are alkyl, for example C ₁ -C ₆ -alkyl, in particular methyl. Accordingly, polydialkylsiloxanes (PDAS) and in particular polydimethylsiloxanes (PDMS) are particularly preferred as modifying units.

The end groups of the polysiloxanes may independently of one another be radicals selected from among alkyl, alkoxy, alkoxyalkyl, alkynyl, aryl or heteroaryl, which may optionally be substituted by halogen, OH, COOH, cycloalkyl, epoxides and / or amino. The polysiloxanes are linked to the base polymer via one or both end groups and / or one or more side chains. The linkage is via at least one reactive group which comprises, for example, OH, SH, COOH, NH ₂ , CN, OCN, anhydride, epoxy and / or halogen groups and reacts with a complementary reactive group on the base polymer Has. There may be one or more reactive groups, preferably one or two reactive groups, at one or both ends of the siloxane. Particularly preferably, two reactive groups are present at one end of the polysiloxane.

The introduction of the modifying units into the base polymer is preferably via modified building blocks, e.g. Monomers comprising the modifying units linked by reactive groups subjected to a polymerization reaction with unmodified building blocks.

In a preferred embodiment, modifying units having a reactive group can be introduced into the polymer to be functionalized by, e.g. initially reacted in a molar ratio of 1: 1 with a trimeric monomer unit, such as a trimeric isocyanate adduct. The resulting compound may then be combined with e.g. react the remaining isocyanate group with the reactive groups of the other monomers and thus form a chain segment of a functionalized polymer.

Polysiloxanes consist of several siloxane units (Si units), which are linked to one another via oxygen atoms. The polysiloxanes may have 20 to 500 Si units, preferably 40 to 400 Si units, more preferably 50 to 200 Si units, and most preferably 60 to 150 Si units. Long-chain polysiloxanes are understood in particular to mean polysiloxanes which have at least 20, more preferably at least 30, even more preferably at least 40, and in particular at least 60, Si units, and preferably up to 500, preferably up to 300, in particular up to 200 and most preferably up to to 150 Si units. In a preferred embodiment, the polysiloxanes are polydialkylsiloxanes, especially polydimethylsiloxanes (PDMS). Suitable polydimethylsiloxanes are, for example

a-Hydroxyalkoxy-co-alkylpolydimethylsiloxane (Formel I),

a-hydroxyalkoxy-co-alkylpolydimethylsiloxanes (formula I),

bis-(Hydroxyalkoxyethyl)-polydimethylsiloxane (Formel II),

bis- (hydroxyalkoxyethyl) -polydimethylsiloxanes (formula II),

a-carboxyalkoxypropyl-u) -butyl-polydimethylsiloxanes (formula III) and

Aminopropylpolydimethylsiloxane (Formel IV). n wird so gewählt, um Kettenlängen im oben genannten Bereich zu geben. R stellt einen Alkylenrest dar, insbesondere einen Alkylenrest mit 1 bis 30, vorzugsweise mit 2 bis 6 Kohlenstoffatomen.

Aminopropylpolydimethylsiloxanes (Formula IV). n is chosen to give chain lengths in the above range. R represents an alkylene radical, in particular an alkylene radical having 1 to 30, preferably having 2 to 6 carbon atoms.

Preferably, mono- or difunctional polydimethylsiloxanes are used. Particularly preferred is an α-difunctional polydimethylsiloxane such as shown in Formula I. FIG. 2 shows by way of example some polydimethylsiloxanes. In a particularly preferred embodiment, the polydimethylsiloxane is o (2,2-dimethylolbutoxy) propyl-n-butylpolydimethylsiloxane. The preparation of such polydimethylsiloxanes is known, as described for example in EP 0 430 216.

Due to their relatively large molecular weight, the polysiloxanes reduce even at higher mass fractions the average molecular weight of the polymers, in particular of polyamide-imides and polyimides, less than smaller molecular building blocks at comparable mass fractions. Therefore, the film properties of the paint are virtually unaffected by incorporation of the modifying units.

For the arrangement of the modifying units, e.g. the polysiloxanes, and the base polymer in the polymer according to the invention, there are various embodiments.

Modification units can form chain end-modified polymers with the base polymer (see, for example, Figure 3a) or a polymer chain of the modifying units with attached units of the base polymer (see, e.g., Figure 3b).

Di- or polyfunctional modifying units can form with units of the base polymer a linker-linked polymer (see, for example, FIG. 3c) or a block copolymer (see, for example, FIG. 3d). Preferably, the Modification unit which has two reactive groups on one end group and no reactive group on the other. This then leads to an insertion of the modifying unit as a linker in the base polymer (see Figure 3c). Alternatively, an α, ω-difunctional unit may be used which has reactive groups at each end group. This then leads to the formation of a block copolymer (see also Figure 3d).

In a preferred embodiment, linker-linked base polymer, especially linker-linked polyamide-imide, is used, with polysiloxane, especially polydimethylsiloxane, which preferably contains from 60 to 80 Si units, e.g. about 65 Si units, acts as a linker between the base polymer units, especially polyamide-imide polymer units (see Figure 3c).

In a further preferred embodiment, end-group-modified base polymer, in particular end-group-modified polyamide-imide, is used, the polysiloxane used, in particular polydimethylsiloxane, preferably containing 60 to 80 Si units, e.g. about 65 Si units, (see Figure 3a).

In another preferred embodiment, side chain functionalized, e.g. aminoalkyl functionalized moieties used with reactive groups, e.g. Isocyanate groups of the base polymer, e.g. a polyamide-imide, react (see also Figure 3b).

In yet another embodiment, functionalized polymers are used wherein α, ω-bis-hydroxyalkyl-terminated polysiloxanes, especially α, ω-bis-hydroxyalkyl-terminated polydimethylsiloxanes, form a block copolymer with the base polymer, eg, a polyamide-imide (see Figure 3d). Particularly advantageous results with regard to the lubricity of the paint are achieved when combinations or mixtures of polymers with a plurality of different modification units having different chain lengths, eg a different number of Si units, are used. Particularly preferred is, for example, the combination of polymers, wherein the first polymer is functionalized with a polysiloxane, in particular a polydimethylsiloxane, with about 60-80 Si units and the second polymer with a polysiloxane, in particular a polydimethylsiloxane, with about 120-140 Si units is functionalized. The mass ratio of the first and second polymers is for example 10:90 to 90:10, preferably 30:70 to 70:30, particularly preferably 40:60 to 60:40, for example 50:50.

In a preferred embodiment, a chain end-modified base polymer, particularly a chain end-modified polyamide-imide (see Figure 3a), wherein the end groups contain 120-140 Si units, e.g. about 132 Si units, with a linker-linked base polymer, especially a linker-linked polyamideimide (see Figure 3c), wherein the polysiloxane linkers contain from 50 to 70 Si units, e.g. about 65 Si units, mixed in a mass ratio of 0.8: 1, 2 to 1, 2: 0.8 and especially 1: 1 mixed.

The proportion of building blocks with modifying units, based on the total polymer, is preferably 2 to 70% by mass, preferably 5 to 50% by mass, and particularly preferably 10 to 30% by mass. A proportion of building blocks with modifier units of 15-25% by mass is most preferred. Polymers having a higher proportion of modifying units can be mixed with polymers containing no modifying units. It is also possible to use mixtures of polymers with modifying units containing different mass% of modifying units with different polymers containing no modifying units. For example, in order to prepare the polymer comprising a base polymer and modifying units, polyols used for the production of polyesters and polyesterimides can react with carboxyl groups and anhydride groups of the modifying units to form esters. Polycarboxylic acids and polycarboxylic acid anhydrides used for the preparation of polyesters, polyamides, polyesterimides, polyamideimides and polyimides can react with OH groups of the modifying units to form esters and with amino groups to form amides. Polyisocyanates used for the preparation of polyesterimides, polyamide-imides and polyimides can react with OH groups of the modifying units to form urethane groups. Polyisocyanates may also react with amino groups of the modifying units to form urea groups.

For the preparation of self-crosslinking polyesters are preferably used as monomers terephthalic acid or

Terephthalic acid dimethyl ester and / or isophthalic acid, glycerol or Trishydroxyethylisocyanurat and / or ethylene glycol used. These monomers can also be used for the preparation of polyesters for crosslinking with capped polyisocyanates.

Polyamides for paints preferably consist of aliphatic dicarboxylic acids and diamines and / or of lactams or aminocarboxylic acids.

As monomers for the production of polyesterimides, terephthalic acid or the dimethyl ester of terephthalic acid, trimellitic anhydride, glycerol or trishydroxyethyl isocyanurate and ethylene glycol are preferably used.

Polyimides may be prepared from tetracarboxylic dianhydrides, preferably pyromellitic dianhydride (PMDA, 1, 2,4,5- Benzene tetracarboxylic dianhydride), and aromatic diisocyanates, preferably using 4,4'-diisocyanatodiphenyl oxide and / or 4,4'-diisocyanatodiphenylmethane (MDI).

Polyamide-imides can be prepared from tricarboxylic acid anhydrides, preferably using trimellitic dianhydride (TMA, 1, 2,4-benzenetricarboxylic anhydride), and aromatic diisocyanates, preferably using 4,4'-diisocyanatodiphenylmethane.

Another object of the invention is a cured lacquer obtainable by curing, in particular thermal curing of a lacquer according to the invention, wherein there are separate areas on the surface of the cured lacquer.

In this case, thermal curing in particular comprises a temperature treatment of 400 ° C. to 700 ° C., preferably of 450 ° C. to 600 ° C., and even more preferably of 525 ° C. to 625 ° C.

A further aspect of the present invention is a process for the preparation of the paint according to the invention, characterized in that a first modified building block, e.g. a monomer or a prepolymer having at least one modifying unit is polymerized with at least one second monomer to obtain a polymer having modifying units which is formulated together with a solvent and optionally additives into a paint for coating surfaces.

In a particularly preferred embodiment, the lacquer according to the invention is prepared by reacting a diisocyanate with a polysiloxane having reactive groups, for example OH, COOH or NH ₂ , and then polymerizing the reaction product, for example a prepolymer, with an acid anhydride. The polymers produced, which are present as colloidal solutions or dispersions, are completed to formulate paints. The polymers are diluted to the desired viscosity with suitable solvents. The coatable lacquers preferably have a viscosity of from 10 to 2500 mPa * s, preferably from 100 to 800 mPa * s and particularly preferably from 200 to 500 mPa * s.

Suitable solvents for the production of paints are, for example, cresols and xylenols which optionally contain a proportion of phenol, glycol ethers, for example an oligoglycol ether, such as, for example, methyl diglycol, glycol ether esters, for example butyl diglycol acetate, propylene carbonate, higher alcohols, for example benzyl alcohol and diacetone alcohol, and higher ketones, such as isophorone. For controlling the viscosity, for example with respect to the solid application, diluents are used, such as aromatic hydrocarbons such as xylenes and C ₃ -C ₅ aromatics, which may also contain alkylnaphthalenes. Examples include Solvesso®100, Solvesso®150, Solvesso®200, Exxon's commercial products.

If polyisocyanates are used for the preparation of the functionalized polymers, preference is given to using polar solvents without reactive hydrogens, for example N-methylpyrrolidone, N-ethylpyrrolidone or N, N-dimethylacetamide. These so-called process solvents are part of the paint.

Further, if necessary, additives such as catalysts and crosslinking partners are added. According to the present invention, the catalysts are, for example, transesterification catalysts, such as, for example, tetrabutyl titanate, or transurethanization catalysts, for example organic tin salts. As crosslinking partners, for example, if polyesters are used as polymers, amounts of capped polyisocyanate, for example mixtures of isomers and derivatives of diisocyanatodiphenylmethane, required for the urethane crosslinking are capped with cresols, to be added. Further additives may be, for example, defoamers and leveling additives.

In a further aspect, the present invention relates to a process for producing a coated surface, characterized in that a first modified building block, e.g. a monomer or a prepolymer is polymerized with at least one modifying unit with at least one second monomer to obtain a polymer having modifying units which is formulated into a paint together with a solvent and optionally additives and the paint is applied to a surface and a bake process is subjected, wherein there are separate areas on the surface of the cured paint.

During the baking process, the film-forming process of the paint according to the invention takes place. The solvents evaporate and, if appropriate, crosslinking reactions take place. On the other hand, a phase separation of the polymer and the modification units takes place during the baking process. As a result, the modifying units orient themselves on the surface of the paint, whereby an improved lubricity is achieved. The phase separation leads to an inhomogeneous surface of the varnish, which becomes clear due to an altered surface structure compared to varnish without modifying units. It is presently believed that the incompatibility of the polymer with the modifying units is due to the tendency of the polymer portion to undergo polar interactions and the tendency of the modifier units to be non-polar interactions.

The paint according to the invention can be applied to a wide variety of surfaces, in particular on metal, glass or plastic surfaces. It is also possible to apply the lacquer according to the invention, comprising functionalized polymer, as the outermost lacquer layer to an article to which one or more conventional lacquer layers have already been applied. The lacquer according to the invention can be used for application as an electrically insulating lacquer on a wire, in particular on a copper wire. Preferably, the wire is an electrical conductor. An electrical conductor according to the present invention is a medium having freely movable charge carriers and therefore capable of carrying electrical current. Preferred electrical conductors according to the present invention are metals or metal alloys, in particular copper and aluminum.

Wires are usually coated in a multi-layer process with different paint materials. In one embodiment, the lacquer according to the invention is therefore applied as an outer layer to a wire which has already been coated with an electrical insulating lacquer without modifying units. The wire on which the lacquer according to the invention is applied as an outer layer may contain as lower layers one or more electrical insulating lacquers without modifying units.

Preferably, the lacquer prepared according to the invention is applied to wires, preferably copper wires, using conventional lacquering machines, which may have a horizontal and vertical arrangement. The wires may have diameters of 0.01 to 10 mm, preferably 0.01 to 3.0 mm, and may be flat or profile wires. The Elektroisolierlack is applied in 2 to 40 dips, preferably 4 to 30, more preferably in 8 to 25 dives on felt or Düsenabstreicher and in convection oven with circulating air temperatures of 400 ° C to 700 ° C, preferably 450 ° C to 600 ° C, more preferably 525 ° C to 625 ° C, baked. In a preferred embodiment, the painting process is continuous and the enameled wires are run at withdrawal speeds of 20 to 250 m / min, preferably 60 to 200 m / min, more preferably 80 to 140 m / min. The paint of the invention can be used for various purposes. Since the coatings of the invention have a low coefficient of friction and thus a low frictional resistance, they can be used advantageously in particular in all applications in which these properties are desired or / and advantageous. Preferably, the use as anti-adhesion and / or anti-fouling coating of surfaces. In one embodiment, the paint of the invention is used as a coating in plain bearings. In a further embodiment, the paint according to the invention is used for vehicles, eg for ship parts, in particular for the ship's hull. Further preferred is the use for tribologically stressed bodies, eg deflection rollers for straps and ropes.

The paint according to the invention has proven to be particularly favorable in marine painting, since it has outstanding anti-fouling properties as well as outstanding fouling-release properties. The polymers described herein comprising a base polymer and modifying units that are incompatible with the base polymer after curing of the polymer can be used especially as binders in marine finishes. In this case, a polyurethane is preferably used as the base polymer. It has been found that by using the paints according to the invention a reduced settlement and a reduced growth of microorganisms on the film surface can be observed.

It is believed that this is due to the chemical composition of the coatings according to the invention, which does not contain nutrients or usable substances necessary for microorganisms. By applying the lacquers according to the invention, such nutrients or usable substances can not be removed from the surface under the lacquer. Thus, the film surface of the coatings of the invention is insufficient suitable as a habitat for marine microorganisms. Only after some time will be through the Absorb a Conditioningfilms, in particular a microorganism-free nutrient film reaches a sufficiently high nutrient density on the surface that microorganisms can settle. However, it has also been found that removal of the microorganisms or cleaning of such surfaces, when coated with paints according to the invention, can be accomplished extremely easily.

Also, the adherence of larger organisms, e.g. Mussels, in particular mussels, is successfully prevented by the lacquer according to the invention. This is attributed to the low coefficient of friction of the paints of the invention, on the basis of which organisms such as shells can not adhere to such a paint surface.

In addition to the application of the coating of marine parts, the coatings according to the invention can also be used generally in coatings which are intended to prevent the growth of organisms or microorganisms.

Currently commercially used anti-fouling or fouling-release coatings are generally based on polysiloxane resins, which are applied in a layer thickness of about 100 to 300 μιτι. Usually, these layers also contain free, chemically unbound silicone oil. The effect of these coatings is based on a low surface energy of the paint layers and the presence of a liquid silicone film. These features make it difficult for microorganisms or organisms, especially fouling organisms such as barnacles, to settle permanently. The adhesive force of the fouling organisms on such paints is so low that often already the shearing force of the water at cruising speed is sufficient to clean the surface. In addition, such conventional fouling-release coatings reduce the frictional drag in the water and thus the fuel consumption of the ships. However, the silicone coatings used so far have several serious disadvantages. Thus, the cured lacquer layers usually contain a proportion of free, not chemically bonded silicone oil, which is released over time to the water. In addition, because of the unbound silicone oil during painting the paint shops are contaminated, making it impossible to process in the same hall conventional paint systems. This disadvantage currently hinders widespread use of the fouling release technology. Furthermore, the previously used silicone coatings are mechanically very unstable and can already be scraped off with a fingernail. For use on ships, which are usually used in harsh environment, this property is very unfavorable.

The use according to the invention of paints comprising a polymer comprising a base polymer and modifying units which are incompatible with the base polymer after curing of the polymer overcomes the disadvantages described above. The polymers used according to the invention have a hard polymer backbone of base polymer combined with chemically bound modifying units, in particular silicone chains. This has the consequence that a mechanically very durable paint film is formed, which shows by quasi-liquid, but chemically bonded silicone chains the fouling-release effect and also the friction-minimizing property of a silicone varnish. Thus, according to the invention, the positive properties of classic paints, in particular a hard, stable paint film, are combined with the positive properties of silicone paints without having to accept the disadvantages of the latter. Due to the fact that modification units according to the invention, in particular polysiloxanes, are covalently bound to the base polymer, there are no free silicone compounds in the paint film. Thus, no silicone is released into the environment and contamination of paint shops is avoided. In particular, durable, hard fouling-release coatings are obtained with the lacquer according to the invention. These fouling-release coatings reduce the frictional drag in the water and thus the fuel consumption of the ships and prevent the adherence of fouling organisms.

The lacquer according to the invention can be applied to any surface, e.g. on a metallic surface or non-metallic surface, e.g. a plastic surface, a ceramic surface or a glass surface. Preferably, the paint according to the invention is applied as an outer layer or layers on a surface which may be coated with one or more paint layers.

Although the surface, which is coated with the paint according to the invention, already has very good lubricity, can be applied as an outer layer additionally an external lubricant.

The invention further relates to the use of a polymer comprising a base polymer and modifying units which, after curing of the polymer, are incompatible with the base polymer as a constituent of a lacquer.

In a further embodiment of the invention, the polymers are in the form of gel particles in the paint. These gel particles contain modifying units, for example long-chain polysiloxanes and in particular long-chain polydimethylsiloxanes, on their surface. The modifying units can protrude outwards (polymer brush structure). Upon contact of a surface containing such a gel particle coating with a mating surface, such as a metallic or non-metallic surface, such as a steel surface or a wound reel of a wire winder, the gel particles are stripped from the paint carrier and are thus available on both of the friction partners. This leads to a further reduction of the Friction resistance and thus to further improve the lubricity.

The object according to the invention is also achieved by a lacquer for coating surfaces comprising a polymer and polysiloxane gel particles. In this embodiment, the advantageous properties of a base polymer, e.g. chemical stability and / or hardness, with the advantageous properties of the modifying units, e.g. Adhesion reduction and / or friction reduction achieved in combination by preventing or at least reducing the release of the modifier units contained in the gel particles into the environment and in particular bleeding by the addition of the modifier units as gel particles.

The polysiloxanes contained as modifier units in the polysiloxane gel particles are incompatible with the polymer after curing of the polymer. They therefore form after curing of the polymer on the surface of the cured paint separate areas. At the same time an immediate leakage of the modifying units is prevented because the polysiloxane gel particles are relatively stable involved in the cured paint.

The added polysiloxane gel particles are, in particular, polydialkylsiloxane gel particles, the alkyl side chains preferably having a length of from 1 to 6 carbon atoms, and more preferably polydimethylsiloxane gel particles. The gel particles are in particular crosslinked gel particles.

As the polymer for the varnish, the base polymers described hereinabove may be used, and in particular polyamideimides, polyesterimides, polyurethanes, polyesters, polyamides, polyimides, polyester-amide-imides, polyepoxides, mixtures or combinations thereof. Particularly preferred are polyamide-imides, polyester-imides and polyurethanes and most preferably polyamide-imides. The polymers can be selected depending on the application of the paint. When using the paint as an anti-fouling coating or fouling release coating, a polyurethane is preferably used as the polymer. When used as Elektroisolierdraht find especially polyamide or or / and polyester imides use.

The invention further relates to a cured lacquer obtained by thermally curing a lacquer comprising a polymer and polysiloxane gel particles. The thermal curing preferably takes place at temperatures of from 400 ° C to 700 ° C, preferably from 450 ° C to 600 ° C and even more preferably from 525 ° C to 625 ° C.

The present invention further relates to a process for the preparation of a lacquer, in which a polysiloxane gel particle dispersion is admixed with a lacquer containing a polymer. The polymer-containing paint may be a conventional paint or a modified paint as described hereinbefore.

The gel particles can be mixed in particular as a friction-reducing component in polymeric coatings and bulk materials, in particular in paints. In particular, in paints based on the polymers described herein, and particularly preferably in electrical insulating paints, for example based on polyamide-imide or polyester-imide, there is a marked reduction in the frictional resistance. These coatings also have very low adhesion.

It has been found that a significant reduction of the frictional resistance in coatings, in particular in polyamide-imide-based coatings, is achieved by the siloxane gel particles according to the invention. Polysiloxane gel particles offer the advantage of an "additive solution", ie they can be mixed in a simple manner with conventional coating systems or paints. It has also been found that during the friction process, a transfer of gel particles from the coating can take place on the article and thus a further reduction in friction, for example compared to steel, is obtained.

The polysiloxane gel particles can also be advantageously used in non-stick and / or anti-fouling coatings.

Conventionally used polydimethylsiloxanes or polydimethylsiloxane-polyether block copolymers are not sufficiently stable in temperature or show a tendency to migrate for many applications. In contrast, polysiloxane gel particles can not migrate due to their crosslinking and have a higher temperature stability than polydimethylsiloxane-polyether block copolymers.

In a preferred embodiment, a polysiloxane gel particle dispersion according to the invention is prepared by crosslinking vinyl group-functionalized polysiloxanes with hydride-functionalized polysiloxanes in a dispersant. Dispersions can be incorporated into a paint, such as an electrical insulating varnish, to thereby provide a low friction paint. But it is also possible to incorporate the gel particle dispersion already in the production of a paint. The crosslinked gel particles orient themselves to the surface of the lacquer layer and lead to a lasting improvement in the lubricity of the surface coated with such a lacquer.

The invention further relates, in particular, to polysiloxane gel particles and to production processes for such gel particles.

In a particularly preferred embodiment, the invention is Polydialkylsiloxan gel particles, wherein the Alkyl side chains preferably have a length of 1 to 6 carbon atoms, and most preferably polydimethylsiloxane gel particles.

The gel particles are preferably prepared as a dispersion of the gel particles in a dispersant. The synthesis of gel particles to form a gel particle dispersion is preferably carried out in polar media. Preferably, the prepolymers or monomers of the gel particles in the dispersion media are not or only slightly soluble. Preferably, as the matrix or dispersant for the dispersion NMP (N-methyl-2-pyrrolidone), NEP (N-ethylpyrrolidone), DMAP (dimethylpyrrolidone), DMAc (dimethylacetamide), DMF (dimethylformamide), water or aqueous solutions or / and DMSO (dimethyl sulfoxide) used. Particularly preferred is a dispersion in N-methyl-2-pyrrolidone.

Such a dispersion of polysiloxane gel particles, in particular of PDAS and more preferably of PDMS gel particles, can be mixed as a component in coating systems and thereby act as a friction-reducing component. The emulsion may itself be stabilized by functional monomers and / or stabilized by an emulsifier.

The gel particles according to the invention can be prepared in various ways. Preference is given to the preparation of a dispersion of crosslinked polysiloxane gel particles, in particular of crosslinked polydialkylsiloxane gel particles and most preferably of crosslinked polydimethylsiloxane gel particles by means of in situ synthesis. The gel particles can also be prepared by addition curing (hydrosilylation) or by emulsion polymerization. The preparation can be carried out in aqueous or non-aqueous matrix.

The starting material used is preferably vinyl-functional siloxane prepolymers in combination with hydride-functional siloxane prepolymers. The reactive groups react via hydrosilylation with each other and form crosslinked polysiloxane gel particles. The crosslinking can be assisted by a suitable catalyst. It is also possible to use only vinyl-functional polysiloxanes and carry out a radical crosslinking, for example by means of a peroxide initiator.

Particularly preferred are dispersions comprising PDMS gel particles in NMP (N-methyl-2-pyrrolidone).

In a preferred embodiment, the gel particles according to the invention consist exclusively of polysiloxanes, in particular polydimethylsiloxanes, which are linked to one another via reactive groups, such as, for example, vinyl groups or hydride groups. However, it is also possible to provide gel particles which contain a core, in particular a SiO ₂ or a polymer core.

The gel particles according to the invention may be used in addition to polymers containing modifying units in order, for example, to achieve a reduction in friction or an anti-fouling. However, it is also possible to use polysiloxane gels instead of modified polymers, i. in conventional paints or coating materials to bring.

In the following, some particularly preferred starting materials for polysiloxane gel particles are described:

Vinyl-terminated polydimethylsiloxanes

worin n eine ganze Zahl von 0 bis 2.000 darstellt. Bevorzugt ist n mindestens 10, mehr bevorzugt mindestens 20, noch mehr bevorzugt mindestens 30 und bis zu 1.000, mehr bevorzugt bis zu 500.

wherein n represents an integer of 0 to 2,000. Preferably, n is at least 10, more preferably at least 20, even more preferably at least 30 and up to 1000, more preferably up to 500.

Vinylmethylsiloxane-dimethylsiloxane copolymers, trimethylsiloxy-terminated

In the formula, the dimethylsiloxane and vinylmethylsiloxane groups can occur in any order, n designates the mol% content of vinylmethylsiloxane and is between 0.5 and 1.5, preferably between 0.8 and 1.2. m indicates the mol% of dimethylsiloxane and is calculated as m = 100 - n.

Vinylmethylsiloxane-dimethylsiloxane copolymers, trimethylsiloxy-terminated, are characterized by their viscosities. Viscosities of 250 cSt to 500,000 cSt are usable according to the invention, in particular viscosities of 1,000 cSt to 100,000 cSt.

Vinyl-functional macromers

Such macromers serve as "dendling ends" and / or for the production of polymer brush surfaces. Examples of suitable vinyl-functional makormers are asymmetric monovinyl-terminated polydimethylsiloxanes, in particular compounds of the formula

worin n eine ganze Zahl von 0 bis 2.000 annehmen kann, n ist vorzugsweise mindestens 10, mehr bevorzugt mindestens 20 und noch mehr bevorzugt mindestens 30 und bis zu 1.000, mehr bevorzugt bis zu 500.

wherein n may take an integer of 0 to 2,000, n is preferably at least 10, more preferably at least 20, and even more preferably at least 30 and up to 1,000, more preferably up to 500.

As hydride-functional siloxane prepolymers, the following structures may preferably be used:

Trimethylsiloxy-terminated methylhydrosiloxane-dimethylsiloxane copolymers, in particular having the general formula

The arrangement of the methylhydrosiloxane and dimethylsiloxane groups in the copolymers is arbitrary, m is in each case the proportion of methylhydrosiloxane and n the proportion of dimethylsiloxane units. Terminated trimethylsiloxy-methylhydrosiloxane-dimethylsiloxane copolymers having a molecular weight of 900 g / mol to a molecular weight of 50,000 g / mol can be used for the preparation of the gel particles according to the invention. Hydride-terminated methylhydrosiloxane-dimethylsiloxane copolymers, in particular having the formula

Dimethylhydrosiloxane and the dimethylsiloxane units can be arranged as desired, m indicates the proportion of methylhydrosiloxane units and n the proportion of dimethylsiloxane. m, ie the mol% proportion of methylhydrosiloxane is preferably 5 to 20, more preferably 7 to 8 n, ie the mol% proportion of dimethylsiloxane is preferably 90 to 95, more preferably 92 to 93. Preferably m, that is to say the mol% proportion of methylhydrosiloxane units, 10 to 90, more preferably 20 to 40 and even more preferably 25 to 30 n, ie the molar proportion of dimethylsiloxane is preferably 50 to 90, more preferably 60 to 80 and most preferably 70 to 75. The molecular weight of the hydride-terminated methylhydrosiloxane-dimethylsiloxane copolymers used is preferably 2,000 to 2,600 g / mole.

Hydride-terminated polydimethylsiloxanes, especially the formula

worin n eine ganze Zahl von 3 bis 300, insbesondere von 4 bis 230 darstellt.

wherein n represents an integer from 3 to 300, especially from 4 to 230.

Crosslinked siloxane gel particles, in particular dispersions of crosslinked PDMS gel particles, can advantageously be used in coating or coating systems be incorporated. Preferably, the preferred herein PDMS gel particle dispersions in NMP are incorporated into conventional NMP-based polyamide-imide lacquers, particularly electro-isolation lacquers. The incorporation can be done for example by means of Dispermate or Ultra-Turaxx. It is also possible to incorporate the gel particles in modified paints, in particular in modified polyamide-imide-Elektroisolierlacke. The gels, in particular in the form of a gel particle dispersion, can also be incorporated into other lacquers and in particular into other electrical insulating lacquers, for example in polyesterimide electrocoating lacquers, polyester electroinsulating lacquers, polyimide electrocoating lacquers, polyamide electrocoating lacquers or / and polyurethane electrocoating lacquers / lacquers.

In a further preferred embodiment, the gel particles are gel particles with a hard silica core, in particular PDMS brush particles with a hard silica core. Silicate particles are used as starting particles. Such particles are preferably made of fumed silica. Preferably, silica particles are used whose surfaces have hydroxyl and / or vinyl groups. Siloxanes are then added to the hydroxyl or / and vinyl groups of the silica particles. This can be achieved by adding a hydride-functional siloxane, optionally in the presence of a catalyst, e.g. of a platinum catalyst. The linkage is via a hydrosilylation reaction. The hydride-functional siloxane used may have one or more Si-H functions. The molecular weight can also be varied and is preferably between 200 and 100,000, more preferably between 500 and 5,000 g / mol.

Alternatively, a hydride-functionalized siloxane can be reacted with a vinyl-functional silazane. Subsequently, the vinyl- or silazane-terminated siloxane can react with hydroxyl groups of silicate particles. Alternatively, it is also possible to use chlorodialkylvinylsilanes, in particular chlorodimethylvinylsilanes. The invention will be explained below with reference to preferred embodiments and figures, which are not intended to limit the scope of the invention.

characters

The phase separation of the base polymers and the modifier units on the surface of the paint will be apparent from Figures 1a and 1b.

FIG. 1a shows an atomic force microscope image of the surface of the lacquer according to the invention based on a polyamide-imide-polydimethylsiloxane block copolymer, the polydimethylsiloxanes having about 63 Si units. The paint is applied to a metal plate.

Significant phase separation between the modifying units, which can be recognized as dark bubbles, and the polymer can be seen on the surface of the paint.

FIG. 1b shows an atomic force microscope image of the surface of a lacquer based on a polyamide-imide-polydimethylsiloxane block copolymer, the polydimethylsiloxane having about 10 Si units. The paint is applied to a metal plate.

A clear phase separation between the polymer and the modifying units is not visible.

The comparison between Figure 1a, wherein a Polydialkylsiloxan with a chain length of 63 Si units and the Figure 1 b, wherein a polydialkylsiloxane was used with a much shorter chain length of 10 Si units, clearly shows that a phase separation only for modifying units according to of the present invention occurs. FIGS. 2a-g show suitable polydimethylsiloxanes for the coating according to the invention.

FIGS. 3a-d show various embodiments of the polymers according to the invention.

FIG. 4 shows a panel coated with a lacquer system according to the invention, which was outsourced in Wilhelmshaven in the North Sea. "Start" (Figure 4a) shows the panel before insertion into the water, "after 1 month" (Figure 4b) shows the panel after one month and "after cleaning" (Figure 4c) shows the panel after cleaning the bottom half with a paint roller.

FIG. 5 shows a panel coated with a coating system according to the invention after two months in the North Sea (FIG. 5a) and after cleaning the lower half with a painting roller (FIG. 5b).

FIG. 6 shows a reference plate after introduction into the North Sea, after one or after two months and after each cleaning.

FIG. 7 shows an atomic force microscopy in D3 image of the surface of a coating of a polyamidimide functionally modified with a polydimethylsiloxane. The bright areas are mobile but fixed siloxane segments.

Examples Example 1

Preparation of a polyamideimide with a 20% proportion of a- (2,2-dimethylolbutoxy) -propyl-n-butylpolydimethylsiloxane-functionalized polymer (modified linker-linked polymer)

In a glass laboratory reactor of 2 l total volume, equipped with an electrical resistance heater with temperature control and control, with a stirrer and a reflux condenser and the introduction of inert gas (nitrogen), 300.0 g of N-methylpyrrolidone (NMP) and 250, Weigh out 0 g of xylene - as process solvent - and 293.5 g of 4,4'-diisocyanatodiphenylmethane (MDI) and slightly heat the reaction mixture. The MDI is dissolved at 45 ° C in the solvent submitted. Then, 104.0 g of a- (2,2-dimethylolbutoxy) -propyl-u) -n-butylpolydimethylsiloxane, which has about 63 Si units added over a period of 15 minutes, the temperature is at 45 ° C held. Then the reaction mixture is heated to 70 ° C and it is stirred at 70 ° C for one hour. It is then cooled to 45 ° C and 218.0 g of trimellitic anhydride (TMA) are added. Then one hour at 45 to 50 ° C is stirred. Thereafter, the temperature is increased with stirring in stages: 30 minutes at 65 ° C, then 30 minutes at 75 ° C, then 60 minutes at 85 ° C, then 60 minutes at 100 ° C, and finally 60 minutes at 130 to 140 ° C. In this case, the reaction product separates carbonic acid from carboxyl groups and isocyanate. The reaction mixture reaches a viscosity (measured on a sample in the plate-and-cone viscometer at 30 ° C.) of 6 Pa s. It is cooled to below 60 ° C and 6.1 g of ethanol added to trap the reaction. The resulting colloidal solution has a solids content of 48% (measured at 1 ^h 130 ° C in a convection oven). The proportion of incompatible polydimethylsiloxane is 20% by mass, based on the total polymer (solids). Comparative Example (VB):

Preparation of a polyamideimide without modifying units

The procedure is the same as described in Example 1, but without the addition of the incompatible polydimethylsiloxane. 300.0 g of NMP and 250.0 g of xylene are weighed into the described laboratory reactor as the process solvent and 293.5 g of 4,4'-diisocyanatodiphenylmethane are dissolved therein at 45 ° C. Then 223.1 g of TMA are added. Then one hour at 45 to 50 ° C is stirred. Thereafter, the temperature is increased with stirring in stages: 30 minutes at 45 ° C, then 30 minutes at 75 ° C, then 60 minutes at 85 ° C, then 60 minutes at 100 ° C and finally 60 minutes at 130 to 140 ° C. , In this case, the reaction product separates carbonic acid from carboxyl groups and isocyanate. The reaction mixture reaches a viscosity (measured on a sample in the plate-and-cone viscometer at 30 ° C.) of 6 Pa s. It is cooled to below 60 ° C. The resulting colloidal solution has a solids content of 42.9% (measured at 1 ^h 130 ° C in a convection oven).

Example 2

Preparation of a Polyamideimide Containing 20% a- (2,2-Dimethylolbutoxy) Propyl (o-n-Butyl Polydimethylsiloxane Functionalized Polymer (Modified Linker-Linked Polymer)

The procedure is the same as described under Example 1. The weighed quantities are listed in Table 1. Example 3

Preparation of a polyamide-imide with 5% a- (2,2-dimethylolbutoxy) -propyl-n-butylpolydimethylsiloxane-functionalized polymer (modified linker-linked polymer)

The procedure is the same as described under Example 1. The weighed quantities are listed in Table 1.

Example 4

Preparation of a Polyamidoimide Containing 20% Aminopropyl Polydimethylsiloxane Functionalized Polymer (Polydialkylsiloxane Having Associated Units of the Base Polymer)

In the apparatus described in Example 1 547.6 g of NMP and 228.0 g of TMA are weighed. The TMA is dissolved with stirring at 70 ° C. Then, 102.5 g of a Aminopropylpolydimethylsiloxans having about 65 Si units added within 15 minutes. It is heated to 120 ° C and then kept at 120 ° C for 1 hour, so that the polydimethylsiloxane can react. It is then cooled to 40 ° C and then 280.0 g of MDI are added within one hour. It is heated to 85 ° C within 2 hours and then to 130 ° C until a viscosity of 6 Pa s (measured in a plate-cone viscometer at 30 ° C) is achieved. Then the reaction mixture is cooled. The resulting product has a solids content of 46.9% (measured at 1 ^h 130 ° C in a convection oven). Example 5

Preparation of a Polyamideimide Containing 20% of 2-Hydroxyethoxypropyl Polydimethylsiloxane-Functionalized Polymer (The Polydimethylsiloxane Has about 132 Si Units, Chain End-Modified Polymer)

The procedure is exactly as described under Example 1. The weighing quantities are listed in Table 1.

Table 1

Examples of polyamide-imides with modifying units and comparative example

Ingredients [g] B1 B2 B3 B4 B5 VB

N-methylpyrrolidone (NMP) 300.0 300.0 300.0 547.6 300.0 300.0

Xylene 250.0 250.0 250.0 - 250.0 250.0

4,4'-diisocyanatodiphenyl 293.5 293.5 293.5 270.0 293.5 146.8 methane (MDI)

 Trimellitic anhydride (TMA) 218.0 218.0 218.0 228.0 224.0 111, 6 a- (2,2-dimethylolbutoxy) -104.0 46.0 22.0

propyl-co-n-butylpolydimethylsiloxane

 Aminopropylpolydimethyl- - - - 102.1 - - siloxane

 2-Hydroxyethoxypropylpolydi- - ~ - 105,0 - methylsiloxane

 NMP - - - 33.1 - -

Ethanol 6.1 6.1 6.1 6.1 6.1

Cleaved C0 ₂ 101, 4 102.4 102.85 93.7 102.8 103.2

 Total 1070.2 1011, 2 986.7 1093.6 1075.2 963.4

Solids [%] (1h 130 ° C) 48.6 45.6 44.3 46.9 48.3 42.9

Proportion of polymer with 20 10 5 20 20 - modifier units [%] Examples 6-11

electrical insulating

 From the polymer solutions described in Examples 1-5 and in the Comparative Example, electrical insulating paints were prepared by adding solvents. The composition of the electrical insulating varnishes is shown in Table 2.

Table 2

electrical insulating

Component [g] Number of Si B6 B7 B8 B9 B10 B 1

 Units in

 the polydimethylsiloxane chain

 Polymer Bspl. 1 approx. 63 488.8 244.4 (20%

 Modification)

 Polymer Bspl. 2 about 63 502.8

(10%

 Modification)

 Polymer Bspl. 3 about 63 488.8

(5%

 Modification)

 Polymer Bspl. 4 about 65 502.8

(20%

 Modification)

 Polymer Bspl. 5 approximately 132 244.4 (20%

 Modification)

 Polymer 502.8 Comparative Example

 N-methyl- 156.2 119.8 98.5 617.5 118.4 82.9 pyrrolidone

 N, N-dimethyl-32.331, 2 29.4 56.1, 30.4, 29.3% acetamide

Total 677.4 653.8 616.7 1176.4 637.6 615.0 Component [g] Number of Si B6 B7 B8 B9 BIO B11 Units in

 the polydimethylsiloxane chain

 Solids [%] 35.1 35.1 35.1 20.0 35.1 35.1 (60 '130 ° C)

 Viscosity 710 860 780 350 660 830 [mPa-s] (plate-cone-viscosity)

Applications of electrical insulation coatings

The electrical insulating varnishes specified in Table 2 were coated on a horizontally operating wire-coating machine with a maximum circulating air temperature of 605 ° C. The bare wire diameter was 0.53 mm, the withdrawal speed 122 m / min. The order was made by dipping with wiping nozzles. There were a total of 10 passages. The order of the first 7 passages consisted of a commercial one

Polyesterimidelektroisolierlack with a nozzle sequence of 560/570/570/580/580/590/590 pm. The following 2 jobs consisted of a commercial Polyamidimidelektroisolierlack with a nozzle sequence of 590/600 pm. The last order consisted of the insulating lacquer according to the invention according to Examples 6-10 or from the lacquer of the comparative example according to Example 11 with a nozzle of 610 pm opening diameter.

Testing the lubricity

In addition to testing the heat resistance and electrical properties, lubricity was determined by two methods.

1. Measurement of surface resistance according to Parusell CoF

When measuring the surface resistance according to Parusell CoF, an enameled wire is placed between a polished steel surface and a surface Steel sled performed. The force measured on the steel slides is measured. The information is given as a friction coefficient (dimensionless). Small values of the coefficient of friction mean low friction (Tensiometrie, see DIN EN 60851).

2. Measurement of frictional resistance according to Scintilla

An enamelled wire is pulled through at high speed under a steel block with a certain bearing surface. It measures the force generated by the friction. Indication in Newton (N).

Table 3 shows the measurement results on the painted wires and on the enameled wire with the comparative example.

Table 3

Measurement results Surface resistances and friction resistances

The measurement results shown in Table 3 show the advantage of the inventive paint (B6-B10) over a paint without modifying units (B1 1). The higher the proportion of modifier units in the polymer (compare B6 20%, B7 10%, B8 5%), the lower the coefficient of friction and frictional resistance. A particularly low coefficient of friction is achieved by mixing in a mass ratio of 50:50 of two polymers with modifying units having a different number of Si units (see B10). Example 12

Preparation of a polydimethylsiloxane-modified polyesterimide (PDMS)

The reaction vessel used is a laboratory reactor (V4A, glass) with indirect heating (eg heat carrier oil) or controllable electrical resistance heating, product temperature control, inert gas inlet, as close as possible edge-stepless, continuously variable stirrer, packed column with head temperature measurement, bridge and descending reflux condenser (all distillate collected) , The column is run as a dephlegmator.

The total amount of polyols (THEIC or glycerol, ethylene glycol), dimethyl terephthalate and 0.3% (based on the yield of total polyesterimide = nfA) butyl titanate are weighed in the order mentioned (see also recipe in Table 4). Subsequently, the slag will admit: approx. 3% on the total weight of Solvesso 150.

Start of the introduction of inert gas (preferably nitrogen, but also carbon dioxide or its mixture with N ₂ usable).

The reaction mixture is heated rapidly to about 160 ° C. Then the temperature is continuously raised to max. Increased 240 ° C. The time scale is determined by the distillation process, the column overhead temperature should not exceed 75 ° C (slightly above the boiling point of methanol, 64.7 ° C). The distilled methanol is collected and determine the amount (density at 20 ° C = 0.7869). The reaction mixture is kept at 240 ° C until no more methanol is obtained. Then it is cooled to below 140 ° C.

Subsequently, amine-functional polydimethylsiloxane is added. Trimellitic anhydride and 4,4'-diaminodiphenylmethane are used as solid mixed, but at least added in varying portions. Then it is carefully heated again. The diimide carboxylic acid spontaneously forms and precipitates. It is added as much Solvesso 150 until the dispersion is easy to stir.

Then it is heated slowly up to 240 ° C. The time measurement is determined by the distillation process, the column should not drown and the column top temperature should not exceed 105 ° C (slightly above the boiling point of water).

From 200 ° C samples are obtained for the measurement of acid number and viscosity. The titration of the acid number is carried out with 0.5 molar, alcoholic KOH against phenolphthalein on a sample dissolved in preneutralized solvent [DIN 53169]. The determination of the dynamic viscosity is carried out with a sample nfA 60% in solvent.

The reaction mixture is kept at 220 ° C until acid number is less than 20 mg KOH / g.

Then the laboratory reactor is switched to short path (descending distillation bridge, preferably with determination of the distillation temperature) and distilled off entrainer and residual water. It is held at 220 ° C until the planned figures are reached.

Then it is strongly cooled to below 170 ° C and about 5 - 10% of the planned amount of solvent added and dissolved and further cooled. Under 130 ° C content of the laboratory reactor is discharged and further dissolved in the bulk of the solvent.

Final figures to be set: nfA (60 min 130 ° C): 70.0 ± 1, 0%

 SZ (solid): 5 - 15 mg KOH / g

 Viscosity (dyn.): _ ± 50 mPa-s (original

Dissolution, 23 ° C) Table 4

recipe:

Example 13

Preparation of a polyamideimide with a 5% proportion of aminopropylmethylsiloxane-dimethylsiloxane copolymer modifier

PDMS modifier:

Mole%

 Code Molecular Weight (Aminopropyl)

 (ABCR) Viscosity [g / mol] MeSiO

 AMS-132 80-100 4500-5500 2.0-3.0

 AMS-152 120-180 7000-8000 4.0-5.0

AMS-162 80-120 4000-5000 6.0-7.0 AMS-132: (2-3% aminopropylmethylsiloxane) -dimethylsiloxane copolymer AMS-152: (4-5% aminopropylmethylsiloxane) -dimethylsiloxane copolymer AMS-162: (6-7% aminopropylmethylsiloxane) -dimethylsiloxane copolymer

In a glass laboratory reactor of 0.5 L total volume, equipped with an electrical resistance heater with temperature control and control, with a stirrer and a reflux condenser and the introduction of nitrogen, 100 g of NMP, 50 g of xylene and 45.6 g of trimellitic anhydride (TMA) are weighed , The TMA is dissolved with stirring at 70 ° C. Then 4.6 g of the PDMS modifier, which has about 70-100 Si units, are added within 15 min. , It is heated to 120 ° C and then held at 120 ° C for one hour to the reaction of the PDMS content. It is then cooled to 40 ° C and then 58.7 g of MDI are added within one hour. It is heated to 85 ° C within two hours, and then to 130 ° C to a viscosity of 5 Pa s (measured in the plate-cone viscometer at 30 ° C) is achieved. It is then cooled to 70 ° C and by addition of 1, 2g ethanol, the still free isocyanate functions are implemented. The resulting product has a solids content of 47-51% (measured at 1 ^h 130 ° C in a convection oven): AMS-132: 51% FK; AMS-152: 47% FK; AMS-162: 48% FK

Application and stoving conditions:

The functionalized with AMS-132 PAI was adjusted by addition of NMP to a FK of 40%, applied with 200μιη, baked at 220 ° C for 10min.

The coated sheet was tested at the IFAM. Example 14

Preparation of the aqueous PU dispersions with a 5% proportion of (2-3% aminopropylmethylsiloxane) -dimethylsiloxane copolymer as modifier

14.1.

 In a reaction apparatus as described in Example 13 36.15g MDI are dissolved in 74g butanone at 82 ° C. Thereafter, 41.27g of Priplast 1838, 1.43g of neopentyl glycol (NPG), 6.46g of dimethanolpropionic acid (DMPA) and 7.93g of cyclohexyldimethanol (CHDM) are added sequentially and this reaction mixture is allowed to react at 82 ° C for 3 hours. After cooling to room temperature, 4.66 g of the modifier AMS-132 is added dropwise over 15 min. After stirring at 50 ° C. for a further 15 minutes, 1.77 g of butanol are added and kept at 82 ° C. for 30 minutes. After addition of 2.14 g dimethylethylethanolamine (DMEA) over 5 min, the mixture is stirred for a further 30 min at 82 ° C. After cooling to 65 ° C 9.64g butyl glycol is added and stirred for 30 min. Thereafter, the addition of 138.6 g of water. The butanone is then distilled off from the resulting dispersion on a rotary evaporator.

The resulting product is adjusted by addition of water to a solids content of 40% (measured at 1 ^h 130 ° C in a convection oven).

The PU dispersion was adjusted to a solids of 25% FK, knife-coated at 200pm wet film thickness and baked at 100 ° C for 10 minutes.

 bidest

14.2.

 In a reaction apparatus as described in Example 13, 52.55 g of MDI are dissolved in 85.9 g of butanone at 82 ° C. Thereafter, 40 g of Priplast 1838, 2.08 g of neopentyl glycol (NPG), 9.38 g of dimethanolpropionic acid (DMPA) and 12.96 g of cyclohexyldimethanol (CHDM) are added successively, and this reaction mixture is allowed to react at 82 ° C for 3 hours. After cooling to room temperature, 6.13 g of the modifier AMS-132 is added dropwise over 15 min. After stirring at 50 ° C. for a further 15 minutes, 2.58 g of butanol are added and kept at 82 ° C. for 30 minutes. After addition of 3.12 g dimethylethylethanolamine (DMEA) for 5 min, the mixture is stirred for a further 30 min at 82 ° C. After cooling to 65 ° C 14g butyl glycol is added and stirred for 30 min. This is followed by the addition of 176.6 g of water. The butanone is then distilled off from the resulting dispersion on a rotary evaporator.

The resulting product is adjusted by addition of water to a solids content of 40% (measured at 1 ^h 130 ° C in a convection oven).

The PUR dispersion was adjusted to a solids of 30% FK, knife-coated at 200pm wet film thickness and baked at 100 ° C for 10min.

 bidest

14.3.

 In a reaction apparatus as described in Example 1), 52.55 g of MDI are dissolved in 90 g of butanone at 82 ° C. Thereafter, 30 g of Priplast 1838, 2.08 g of neopentyl glycol (NPG), 9.38 g of dimethanolpropionic acid (DMPA) and 13.68 g of cyclohexyldimethanol (CHDM) are added successively, and this reaction mixture is allowed to react at 82 ° C for 3 hours. After cooling to room temperature, 5.66 g of the modifier AMS-132 is added dropwise over 15 min. After stirring at 50 ° C. for a further 15 minutes, 2.58 g of butanol are added and kept at 82 ° C. for 30 minutes. After addition of 3.12 g dimethylethylethanolamine (DMEA) for 5 min, the mixture is stirred for a further 30 min at 82 ° C. After cooling to 65 ° C 14g butyl glycol is added and stirred for 30 min. Thereafter, the addition of 164.4g of water. The butanone is then distilled off from the resulting dispersion on a rotary evaporator.

The resulting product is adjusted by addition of water to a solids content of 40% (measured at 1 ^h 130 ° C in a convection oven).

The PUR dispersion was adjusted to a solids of 30% FK, knife-coated at 200pm wet film thickness and baked at 100 ° C for 10min.

 est

Example 15

Attempt to fouling-release effectiveness of the coating according to the invention in the North Sea

Two panels (Alu1 and Alu2) were coated with the paint system and outsourced in Wilhelmshaven in the North Sea. After one or two months, the bottom half of the panels were cleaned with a roller to check for easy removal of the growth. For comparison, a parallel outsourced reference sample was tested.

Conclusion of the experiment:

From the coating according to the invention, the growth can be easily and completely removed, not from the reference coating (see FIGS. 4 to 6). Example 16

Synthesis protocol of an in situ synthesis of a PDMS gel particle dispersion

The disperse phase (NMP position 1) and a suitable emulsifier (position 2) are placed in a 2 liter glass reactor with an armature stirrer and reflux condenser which is as close to the wall as possible.

The vinyl functional PDMS prepolymer (position 3) is mixed with a suitable catalyst (position 4) and placed in a dropping funnel.

The hydride functional PDMS prepolymer (position 5) is filled in another dropping funnel.

Both prepolymers are added dropwise over about 10 minutes with vigorous stirring.

(By choosing the catalyst, the necessary reaction temperature can be varied from room temperature to over 100 ° C.)

It is stirred vigorously for a further 5 hours, then stirred slowly for 20 hours.

Example recipe GP2002:

 SUM: 100.00 100.00

The resulting dispersion of crosslinked PDMS gel particles is incorporated into conventional NMP-based polyamideimide electro-isolation varnish (e.g., by Dispermat or Ultra-Turaxx).

Percentage of dispersion in the "blend":

 1 - 75% (PDMS gel particle dispersion); preferably 5-20%; more preferably about 10%

Advantages of this synthesis and the obtained PDMS gel particles:

By functionality and molecular weight of the prepolymers, the mesh size of the crosslinked gel particles can be controlled. By using mono-vinyl-functional prepolymers, "dendling ends" (free polymer ends) can be introduced and gel particles with PDMS brush surface can be produced.

By using an excess of di-vinyl functional prepolymers, "dendling ends" (free polymer ends) can also be introduced and gel particles with PDMS brush surface can be created.

Due to the crosslinking within the gel particles, the migration ability of the siloxanes is prevented.

In situ synthesis in NMP allows the obtained dispersion to be incorporated directly into an NMP-based electrical insulating varnish.

The obtained Dipersion cross-linked PDMS gel particles can be incorporated as an additive in an NMP-based Elektroisolierlack, due to "missing" polyether segments, the temperature stability compared to conventional slip additives (polyether-polydimethylsiloxane copolymers) is increased.

Example 17

Application experiments with PDMS gel particle dispersions:

Table 5 shows mixtures of electrical insulating varnishes and PDMS gel particles for the application tests with subsequent friction tests.

The PDMS gel particle dispersions were incorporated by Ultra-Turaxx into a conventional NMP-based polyamideimide electro-insulating varnish and into a modified varnish of polyamide-imide-polydimethylsiloxane-block-co-polymers with 20% PDMS content. Table 5

 Testing the lubricity

 In addition to testing the heat resistance and electrical properties, lubricity was determined by two methods.

1. Measurement of surface resistance according to Parusell CoF

 When measuring Parusell CoF surface resistance, an enameled wire is placed between a polished steel surface and a resting steel carriage. The force measured on the steel slides is measured. The information is given as a friction coefficient (dimensionless). Small values mean less friction (Tensiometrie, see DIN EN 60851).

2. Measurement of frictional resistance according to Scintilla

 An enamelled wire is pulled through at a higher speed under a steel block with a certain contact surface. The force generated by the friction is measured in Newtons (N).

Claims

claims A surface-coating varnish containing a polymer comprising a base polymer and modifying units that are incompatible with the base polymer after curing of the polymer. 2. Paint according to claim 1, characterized in that there are separate areas after curing of the polymer on the surface of the cured paint. 3. Varnish according to claim 1 or 2, characterized in that the modifying units are long-chain polysiloxanes, preferably polydialkylsiloxanes. 4. Paint according to claim 3, characterized in that the polysiloxane has from 20 to 500 Si units. 5. Varnish according to one of the preceding claims, characterized in that the base polymer is selected from the group consisting of polyamide-imides, polyester-imides, polyurethanes, polyesters, polyamides, polyimides, Polyesteramidimiden, polyepoxides, mixtures or combinations thereof. 6. Paint according to claim 5, characterized in that the base polymer is a polyamide imide. 7. Paint according to one of the preceding claims, characterized in that the proportion of building blocks with modifying units 2-70 mass% based on the total polymer. 8. Cured lacquer obtainable by thermally curing a lacquer according to any one of claims 1 to 7, wherein there are separate areas on the surface of the cured lacquer. Process for the preparation of a paint according to any one of Claims 1 to 7, characterized in that a first modified building block, e.g. a monomer or a prepolymer is polymerized with at least one modifying unit with at least one second monomer to obtain a polymer having modifying units which is formulated into a varnish together with a solvent and optionally additives. 10. The method according to claim 9, characterized in that a diisocyanate is reacted with a polysiloxane having reactive groups and the reaction product is then polymerized with an acid anhydride. A process for producing a coated surface, characterized in that a first modified building block, e.g. a monomer or a prepolymer is polymerized with at least one modifying unit with at least one second monomer to obtain a polymer having modifying units which is formulated into a paint together with a solvent and optional additives and the paint is applied to a surface and a stoving process is subjected, wherein there are separate areas on the surface of the cured paint. 12. Use of the paint according to any one of claims 1 to 7 as an anti-adhesion and / or anti-fouling coating of surfaces. 13. Use according to claim 12 on a metallic or non-metallic surface. 14. Use according to claim 12 as a coating in plain bearings and / or for pulleys for straps and ropes. 15. Use according to one of claims 12 to 14, characterized in that the lacquer is applied as an outer layer or layers on a surface which is coated with one or more lacquer layers. 16. Use according to claim 12 as an anti-fouling coating and / or fouling-release coating on a ship's hull. 17. Use of the paint according to one of claims 1 to 7 as Elektroisolierlack for application to a wire. 18. Use of a polymer comprising a base polymer and modifying units which, after curing of the polymer, are incompatible with the base polymer as a constituent of a varnish. A paint for coating surfaces comprising a polymer and polysiloxane gel particles. 20. The paint of claim 19, characterized in that there are separate areas after curing of the polymer on the surface of the cured paint. 21. The paint of claim 19 or 20, comprising polydialkylsiloxane gel particles, in particular polydimethylsiloxane gel particles. 22. The paint of claim 19, wherein the polymer is selected from the group consisting of polyamideimides, polyesterimides, polyurethanes, polyesters, polyamides, polyimides, polyesteramidimides, polyepoxides, mixtures or combinations thereof is selected. 23. Lacquer according to claim 22, characterized in that the polymer is a polyamideimide. 24. Cured lacquer obtainable by thermal curing of a lacquer according to one of claims 19 to 23. 25. A method for producing a paint according to any one of claims 19 to 23, characterized in that a polysiloxane gel particle dispersion and a polymer-containing paint are mixed. 26. The method according to claim 25, characterized in that it is the paint containing a polymer is a conventional paint or a paint according to any one of claims 1 to 7. 27. A polysiloxane gel particle dispersion comprising polysiloxane gel particles in a dispersant. 28. Polysiloxane gel particle dispersion according to claim 27, characterized in that it comprises polydialkylsiloxane gel particles, in particular polydimethylsiloxane gel particles. 29. Polysiloxane gel particle dispersion according to claim 27 or 28, characterized in that the dispersant is selected from N-methylpyrrolidone, N-ethylpyrrolidone, dimethylpyrrolidone, dimethylacetamide, dimethylformamide, water or / and dimethyl sulfoxide. 30. A process for preparing a polysiloxane gel particle dispersion according to any one of claims 27 to 29, characterized in that vinyl-functional polysiloxanes are reacted with hydride-functional siloxanes in a hydrosilylation reaction in a dispersant. 31. Use of a paint according to any one of claims 19 to 23 as anti-sticking and / or anti-fouling coating of surfaces. 32. Use according to claim 31 on a metallic or non-metallic surface. 33. Use according to claim 31 as a coating in plain bearings and / or for deflection rollers for straps and ropes. 34. Use according to one of claims 31 to 33, characterized in that the lacquer is applied as an outer layer or layers on a surface which is coated with one or more lacquer layers. 35. Use according to claim 31 as an anti-fouling coating on a ship's hull. 36. Use of the paint according to any one of claims 19 to 23 as Elektroisolierlack for application to a wire. 37. Use of polysiloxane gel particles as a constituent of a lacquer.